Trisazo dyestuffs, their copper compounds, and their manufacture



Patented Aug. 7, 1945 TRISAZO DYESTUFFS, THEIR COPPER COM- PQUNDS, THEIRMANUFACTURE .7 AdolfaKrebser, Riehen, near Basel, and Werner Bossard,Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, SwitzerlandNo Drawing. Application October 28, 1941, Serial No. 416,900. InSwitzerland August 2, 1940 6 Claims. (Cl. 260173) It has been foundthat,,ya1ua cd p e trisazodyestuffs are obtained: by coupling thetetrazo compound ofa diamin'e containing 2 benzene nucleiwhich' arelinked'by a member of the class consisting of -NH--CO and NH--CO- NHonly 0n.one half side with an o-hydroxyphenyl carboxylic acid, thencombining the obtained diazoazo compound with" an amine or an aminosulphonicacid of thenaphthalene series coupling in para-position,and-containing in or thoposition to the diaz'otable amino group asub-*stituent capable of-forming' metal complex compounds, furtherdia'zoti'sing the "amino disazo dyestuff, coupling thela'tte'rwith a Nacyl-substitution product ofthe2-ainino-6-hydroxynaphthalene-8-sulphonic acid and converting thetrisazo dyestufi, according't'o usual methods in substance or on thefiber into the copper complex compounds.

Instead of the ttetrazo compound of the diamine E; mentioned above,there may be used as well (as is wherein A stands for the radical of atetrazotised diamine containing two benzene nuclei which are linkedbyemember of the class consisting of -NI -I-,-C'O-- and -NHCO-NH-, Btands for the radical of an" ,ortlio hydroxy carboxylic "acid reen.

of the benzene series, Cs'tands for the radical of a diazotizedl-amino-2-naphtho1ether which may be substituted by a sulphonic acidgroup in the 6- or 'i-position, and D stands forthe radical of a 2-acylamino-6-naphtholP8-sulphonic acid.

The new dyestuffs possess, also when coppered,

substantive properties and dye greenfto olive shades which aredistinguished by a remarkable fastness to light. Ifv desired,-the newdyestuficopper. compounds can also still be further coppered ontheflbre'.

i The following example illustrates the invention,

the parts being by weight.

" EXAMPLE 24.1. arts of 4.4-diamino diphenyl urea are, as known,'diazotised and coupled at 0 C. at one side with 14 parts of salicylicacid in the presence of magnesia. Then it is made acid to litmus bymeans of hydrochloric acid and. further coupled in acetic acid conditionwith 25.3 parts of l-amino- 2 hydroxynaphthalene methylether-G-sulphonicacid. The disazo dyestufi is, in acid condition, isolated, dissolved in1500 parts of water and caustic soda lye, mixed with 7.5 parts of sodiumnitrite and diazotised by pouring thereinto at 5 C. 80 parts ofconcentrated hydrochloric acid. The diazonium compound filtered oil" issuspended in ice-water and then coupled at 0 C. with 28.1

,parts of 2eacetylamino-6-hydroxynaphtha1ene-8- sulphonic acid which hasbeen dissolved in 200 parts .ofwater with 200 parts of pyridine and 20.parts of sodium carbonate. The finished dyestufi is salted out,filteredaand dried in vacuo. It dyes cotton from the Glaubers salt bathin green shades which are transformed, by after treatment with coppersalts on vthefibre, into a fast'olive- A number of further examples areenumerated in the following table.

Table Properties A B O D (zgloration of C e copper dates: cotton poundor atter-coppered on the fibre lA-dialninobenzene Salicylic acidl-amino-Z-hydroxynaptha- 2-benz0ylamino-fi-hydroxy- GreenGreenishlene-methylether-o-sulnapthalenc-B-sulphonic grey. phonic acid.acid. 4.4-diaminodiphenylurea. m-Cresotinicacid .do2-acetylcmino-6-hydroxydo Olive-green,

nagthalene-S-sulphonic acl 1.3-diaminobenzene Salicylic acid1-amino-2-hydroxynapths- ..do Blue-green.. Green. leneethylether-7-sulphonic acid. (N)-3-amiuobenzoy1-l.4- dol-amino-2-hydroxy-napthado ..do Do,

diaminobenzene. lene methylether-B-sulphonic acid.1.4-diaminobenzene-2-sul- ,do l-amino-2-hydroxynaptha- .do Green Grey.

phonic acid. lene ethyl-ether. 1,3-diaminbenzene doi-amino-2-hydroxynaptha- 2-malemylamino-8-hydroxy- Olive green Green.

lone methylether 6 sulnaphthalene -8 sulphonie phonic acid. acid.lAdiaminobenzene o-Cresotinic acid do 2 chloroacetylamino 6 Grey Olive.

I ligdroxynapthalene-fl-sul- U p onicacid. (N)-4-aminobenzoy1-1.4-Salicylic acid do 2-benzoylamino-fi-hydroxy- Blue-green Green.

- diaminobenzene 2 sulnapthalene-8-sulphonic phonic acid. acid.

What we claim is: 1. The trisazo dyestuffs having in the free state thefollowing formula:

wherein each Bzstands for a benzene nucleus, X stands for a member ofthe group consisting of NH CO and NHCO-NH-1-, an -NH of the member Xbeing connected to Bz (2), B stands for the radical of anortho-hydroxy-carboxylic acid of the benzene series, C stands fortheradical of a member of the group consistingof a diazotised1-amino-2-naphtho1ether-6-su1- phonic acid and a diazotisedl-amino-Z-haphthol- 'ether-7-sulphonic acid, and D stands for theradical of a 2-acylamino-6-naphthol-8-sulphonic acid, beingin form oftheir sodium salts dark powders, soluble in water and, in combinationwith a copper yielding compound, dyeing cotton generally from green toolive shades of good fastness properties; v

' 2-. Thetrisazo dyestufis'of the formula wherein each Bz stands for abenzene nucleus,

X stands for a member of the group consisting of -.-NH--.CO- and--NHCONH--, an -NH--:of the member X being connected to Bz(2), B standsfor the radical'oian orthohydroxy-carboxylic acid ofthe benzene series,and Z=stands fora-member of the'groupconsisting of H and S,O3H,'beinginform of their sodium" salt dark powders, soluble in water, dyeing,when coppered, cotton green-to olive shades of good fastness propertiesto light.

3. The trisazo dyestufis having in the free state the following formulaIiBz NH to- I 0 .alkyl OH Ba I wherein each Bz means a benzene nucleus,3

\ stands for the radical of an ortho-hydroxy-cerboxylic acid of thebenzene series and Z stands for a member of the group consisting of Hand 803K, being in form of their sodium salts dark powders, soluble; inwater, dyeing, when coppered, cotton green toolive shades of goodfastness properties to light. 4. The trisazo dyestufi having in the freestate the following formula being in form of the sodium salt, a darkpowder '75 dyeing cotton green shades which, on coppering,

turn to olive shades of good fastness properties. 5. The trisazodyestuffs having in the free state the following formula wherein each Bzmeans a benzene nucleus, B

stands for the radical of an ortho-hydroxy-carboxylic acid of thebenzene series and Z stands for a member of the group consisting of Hand SOsI-I, being in the form of their sodium salts dark powders,soluble in water, dyeing, when coppered, cotton green shades of goodfastness properties.

6. The trisazo dyestufl having in the free state the following formulaSOIH NELGOOH: being in form of the sodium salt a dark powder soluble inwater, dyeing, when coppered, cotton green shades of good fastnessproperties.

ADOLF KREBSER. WERNER BOSSARD.

